The class of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon is now well known in the art. Such polymers are broadly represented by the repeating formula ##STR1## wherein A is derived from a moiety of at least one ethylenically unsaturated hydrocarbon polymerized through the ethylenic unsaturation thereof.
A number of processes are known for producing such polymers which are now becoming known as polyketones or polyketone polymers. The processes typically involve the use of a catalyst composition formed from a compound of a Group VIII metal selected from palladium, cobalt or nickel, the anion of a strong non-hydrohalogenic acid and a bidentate ligand of phosphorus, nitrogen or sulfur. In van Broekhoven et al, U.S. Pat. No. 4,843,144, there is described a process for producing linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon which employs a catalyst formed from a palladium salt, the anion of a non-hydrohalogenic acid having a pKa of below about 6 and a bidentate ligand of phosphorus. Van Broekhoven et al, U.S. Pat. No. 4,880,903 describe a process of producing polyketone terpolymers of carbon monoxide, ethylene and other ethylenically unsaturated hydrocarbons such as propylene. The process typically utilizes a catalyst composition formed from a compound of a Group VIII metal selected from palladium, cobalt or nickel, the anion of a strong non-hydrohalogenic acid and a bidentate ligand of phosphorus, arsenic or antimony. Similar processes using bidentate ligands of nitrogen are disclosed in U.S. Pat. No. 4,851,582 and processes using bidentate ligands of sulfur are described in U.S. Pat. No. 4,965,341.
The nature of the polyketone polymerization process is variable. The above van Broekhoven et al patents employ a catalyst composition which is homogeneous, i.e., soluble in the polymerization media which includes a reaction diluent. Alternatively, the polymerization catalyst may be heterogeneous wherein the catalyst composition is supported on a carrier which is substantially insoluble in the reaction mixture. U.S. Pat. No. 4,778,876 and U.S. Pat. No. 4,806,630 describe the use of supported catalyst compositions in gas-phase processes. U.S. Pat. No. 5,055,552 and copending U.S. patent application Ser. No. 716,487, filed Jun. 17, 1991, describe the use of supported catalysts in slurry-phase processes wherein the catalyst is produced by reaction of the catalyst components with the carrier. Although a variety of supports or carriers is used in such processes, there is no discussion within these references of any particular benefits to be gained by use of a support of any particular physical dimensions or properties.
The use of a supported catalyst broadly has certain benefits when such catalysts are used in gas-phase polymerization processes. Conducting the process in the gas phase with a supported catalyst avoids the processing steps such as filtration or centrifugation which are necessary when the polyketone polymer is produced in the presence of a homogeneous catalyst and a reaction diluent. It would be of advantage to provide an improved gas-phase process for the production of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon which employs an improved supported polymerization catalyst.